Research Article |
Corresponding author: Raffaella Balestrini ( balestrini@irsa.cnr.it ) Academic editor: Alessandro Campanaro
© 2019 Raffaella Balestrini, Carlo Andrea Delconte, Andrea Buffagni, Alessio Fumagalli, Michele Freppaz, Italo Buzzetti, Enrico Calvo.
This is an open access article distributed under the terms of the Creative Commons Attribution License (CC BY 4.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.
Citation:
Balestrini R, Delconte C, Buffagni A, Fumagalli A, Freppaz M, Calvo E, Buzzetti I (2019) Dynamic of nitrogen and dissolved organic carbon in an alpine forested catchment: atmospheric deposition and soil solution trends. In: Mazzocchi MG, Capotondi L, Freppaz M, Lugliè A, Campanaro A (Eds) Italian Long-Term Ecological Research for understanding ecosystem diversity and functioning. Case studies from aquatic, terrestrial and transitional domains. Nature Conservation 34: 41-66. https://doi.org/10.3897/natureconservation.34.30738
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A number of studies have reported decreasing trends of acidifying and N deposition inputs to forest areas throughout Europe and the USA in recent decades. There is a need to assess the responses of the ecosystem to declining atmospheric pollution by monitoring the variations of chemical species in the various compartments of the forest ecosystem on a long temporal scale. In this study, we report on patterns and trends in throughfall deposition concentrations of inorganic N, dissolved organic N (DON) and C (DOC) over a 20-year (1995–2015) period in the LTER site -Val Masino (1190 m a.s.l.), a spruce forest, in the Central Italian Alps. The same chemical species were studied in the litter floor leachates and mineral soil solution, at three different depths (15, 40 and 70 cm), over a 10-year period (2005–2015). Inorganic N concentration was drastically reduced as throughfall and litter floor leachates percolated through the topsoil, where the measured mean values (2 µeq L-1) were much lower than the critical limits established for coniferous stands (14 µeq L-1). The seasonal temperature dependence of throughfall DOC and DON concentration suggests that the microbial community living on the needles was the main source of dissolved organic matter. Most of DOC and DON infiltrating from the litter floor were retained in the mineral soil. The rainfall amount was the only climatic factor exerting a control on DOC and N compounds in throughfall and forest floor leachates over a decadal period. Concentration of SO4 and NO3 declined by 50% and 26% respectively in throughfall deposition. Trends of NO3 and SO4 in forest floor leachates and mineral soil solution mirrored declining depositions. No trends in both DON and DOC concentration and in DOC/DON ratio in soil solutions were observed. These outcomes suggest that the declining NO3 and SO4 atmospheric inputs did not influence the dynamic of DON and DOC in the Val Masino forest. The results of this study are particularly relevant, as they are based on a comprehensive survey of all the main compartments of the forest ecosystem. Moreover, this kind of long-term research has rarely been carried out in the Alpine region.
Nitrate, N-saturation, throughfall, litter floor, DON, LTER
Since the Industrial Revolution, forests have been exposed to elevated atmospheric fluxes of nitrogen (N) and sulphur (S), if compared to natural background. Throughout the second half of the 20th century, this has caused phenomena of N saturation and soil acidification in large areas of Europe and the United States (
In order to assess responses of the ecosystem to the decline of N atmospheric loads it is important to investigate the transformation of N and C forms in the various compartments of the alpine forest ecosystem. Indeed, substantial changes of chemical species occur as rainfall passes through the tree canopies, reaches the forest floor and then percolates into the deeper layers of soil. Although long- term monitoring of soil solution chemistry is a valuable tool to evaluate abatement strategies and to verify the effective recovery of forest ecosystem from long-term inputs, this kind of study is rarely carried out in the Alps (
The overall objective of the present study is to evaluate the biogeochemistry of N species and DOC at Val Masino forest, a remote site in the Italian central Alps, belonging to the Italian LTER network (LTER-Italy: www.lteritalia.it) and to the ICP Forests programme (www.icp-forests.org), launched in 1985 under the Convention on Long-Range Transboundary Air Pollution (CLRTAP) of the United Nations Economic Commission for Europe (UNECE, www.unece.org). Since 1994, several studies have been carried out in this area in order to investigate the effects of S and N atmospheric deposition on the biological component of the ecosystems, first of all in the forest community (
The study area Val Masino (46°14'31.44"N, 9°35'51.51"E) is located at 1190 m a.s.l. in the upper watershed of the Masino River in the Central Alps (Northern Italy) (Figure
Depth | Clay | Silt | Sand | pH | Exchangeable acidity | Corg | TN | C/N |
---|---|---|---|---|---|---|---|---|
cm | % | % | % | (CaCl2) | cM kg-1 | g kg-1 | g kg-1 | |
-4–0 | 4.3 | 3.6 | 381.1 | 15.0 | 25.4 | |||
0–10 | 1.4 | 9.5 | 89.1 | 3.9 | 6.6 | 80.1 | 5.6 | 14.3 |
10–20 | 1.5 | 15.2 | 83.3 | 4.3 | 3.9 | 45.7 | 3.7 | 12.5 |
20–40 | 1.2 | 16.3 | 82.5 | 4.3 | 3.3 | 37.9 | 3.1 | 12.1 |
40–80 | 1.2 | 16.7 | 82.1 | 4.5 | 2.6 | 33.7 | 2.4 | 14.2 |
All sampling activities and chemical analyses were conducted according to the international procedures adopted within the International Co-operative Programme on Assessment and Monitoring of Air Pollution Effects on Forest (ICP Forests) (UN-ECE 1998).
Since 1994 the experimental area has been equipped with 9 bulk rainwater samplers - polyethylene buckets (5L volume) with an 18 cm ID funnel - uniquely identified by a number and placed one meter above the ground. In the winter season 5 snow samplers (56 cm ID) replaced those for rain. Samplings and analyses of atmospheric deposition have been conducted on a weekly basis from 1995 to 2015, except for the 2007–2008 two-year period during which chemical analyses were conducted on bi-weekly combined samples. At the end of each 7-day sampling period, depositions collected by the throughfall samplers were combined to form one homogeneous sample and stored at 4 °C until shipping to laboratory. In 2007 and 2008, prior to chemical analyses, weekly samples were combined proportionally to obtain a 500 ml bi-weekly sample.
The monitoring of soil solution chemistry, instead, was carried out in two different periods. A first survey, from 1999 to 2001, was followed by a second longer investigation starting in 2005 and ending in 2015. The sampling system consisted of tension lysimeters made of 1 µm porosity ceramic cup connected via a plastic tube, to a 2L glass bottle to which the vacuum was applied. In 1998, six sampling points were equipped with lysimeters collecting water at 30 and 50 cm depth. During autumn 2005, changes were made to the experimental plan. Fifteen lysimeters collecting soil solutions at 15, 40, and 60–70 cm depth were placed at five sampling points. In order to monitor forest floor leachate, 3 zero-tension lysimeters, concave-shaped steel plates, were placed below the litterfall at 3 sampling points representative for different plant species and slope. These lysimeters worked by gravity and collected the precipitation passing through the canopy and the forest floor. Since soil disturbance due to lysimeter installation may affect water chemistry, samples collected in a first period (6–12 months) were discarded and regular sampling of soil solution began in 1999 and again in May 2006. Due to snow cover and the possibility of water freezing inside the tubes and the bottles, soil solution and forest floor leachates were mostly sampled from April to November. Analyses on soil solution and forest floor leachates were performed on bi-weekly samples.
The analysis was performed on filtered samples (0.40 µm), except for measurements of electrical conductivity (EC), pH, and total nitrogen (TN), for which unfiltered samples were used. Total organic nitrogen (TON) was obtained from TN minus total inorganic nitrogen (TIN). During 2005 we determined both total and dissolved N (TDN) and from 2006 to 2013 only TDN was assayed. Dissolved organic carbon (DOC) and total aluminum analyses were performed by high temperature catalytic oxidation (IR detection) and ICP-OES respectively.
Major anions (Cl, SO4, NO3) and cations (Ca, Mg, Na, K) were determined using suppressed ion chromatography, whereas NH4 and total N were assessed by UV/VIS spectrophotometry.
For alkalinity we used a two end-points potentiometric titration with HCl 0.01M. The whole references for analytical methods and instrumentation used are presented in Suppl. material
The quality assurance controls included the participation in the ICP Forest ring tests, ICP Waters (organized by NIVA http://www.icp-waters.no/publications/), EMEP (https://www.nilu.no/projects/ccc/intercomparison/index.html) and WMO-GAW (http://www.qasac-americas.org/lis/) interlaboratory comparison programme. We used routine quality control charts based on certified or internal standards.
We used volume-weighted means (VWM) for monthly and annual throughfall concentration and arithmetic mean for forest floor and soil solution monthly concentration. In order to obtain an annual estimate of the amount of soil water at each depth we applied the mass balance approach for sodium (Na) (
Statistical significance of trends and the slope of the derived relationships were assessed by means of Seasonal Kendall Test and Theil-Sen’s slope estimator, respectively (
Figure
VWM concentrations of nitrate, ammonia, DOC and DON in water samples collected in different compartments at Val Masino site. Error bars represent the standard deviation. THR = throughfall depositions; FF = forest floor leachate; TS (topsoil) = soil solution at 15 cm depth; SS (subsoil) = soil solution at 40 cm depth; DS (deep soil) = soil solution at 70 cm depth.
The highest mean annual concentration of NO3 occurs in throughfall (27.0 ±9.7 µeq L-1, n = 21) and forest floor leachates (25.3 ±12.8 µeq L-1, n = 10). A drastic decline of NO3 is evident through the mineral soil where the concentrations ranged from 1.5 – 2.4 µeq L-1. The reduced nitrogen form, NH4, showed an analogous pattern with higher values in the throughfall (17.7±5.0 µeq L-1, n = 21) and forest floor leachate (22.8 ±9.8 µeq L-1, n = 10) and concentrations close to the detection limit in the soil solutions. A more homogenous pattern characterised SO4, which showed a restricted range of values, between a minimum mean value of 18.4±7.1 µeq L-1 (n =10) measured in the forest floor and a maximum of 35.7±38.9 µeq L-1 (n = 14) at 40 cm depth in the mineral horizon (Suppl. material
The forest floor was the principal source of base cations (BC), DON and DOC, which reached concentrations much more elevated in this leachate than in the other matrices. BC and DON concentrations followed the order FF>THR>TS>SS>DS, while for DOC the order was FF>TS>THR>SS>DS.
DON was the main form of N in all the analyzed matrices constituting the 45%, 70%, 85%, 83% and 68% in the throughfall, forest floor leachate, soil solution at 15, 40 and 70 cm depths, respectively.
Al concentrations measured in the last decade showed the highest mean concentration in the topsoil (468±94.1 µg L-1, n = 11) to then gradually decrease with depth; the mean value was 247±51.1 µg L-1 (n = 9) (Suppl. material
The Pearson product-moment correlation coefficients between monthly concentrations of the main chemical species within each environmental matrix are shown in Table
Pearson correlation between monthly average concentration of throughfall depositions (THR), forest floor leachate (FF), topsoil (TS = topsoil solution at 15 cm depth), subsoil (SS = subsoil solution at 40 cm depth) and deep soil (DS = deep soil solution at 70 cm depth). Significance: * = p ≤ 0.05; ** =p ≤ 0.01; *** = p ≤ 0.001; ns: not significant.
THR | FF | TS | SS | DS | |
---|---|---|---|---|---|
NO3:SO4 | 0.771*** | 0.775*** | ns | ns | ns |
NO3:NH4 | 0.850*** | 0.668*** | ns | ns | ns |
NH4:SO4 | 0.696*** | 0.400*** | ns | ns | ns |
DON:DOC | 0.533*** | 0.603*** | 0.461*** | ns | ns |
DOC:BC | 0.760*** | 0.529*** | 0.453*** | 0.462*** | 0.257* |
DON:BC | 0.533*** | 0.444** | 0.437*** | ns | 0.257* |
DOC:H+ | 0.259*** | 0.361* | 0.443*** | ns | ns |
DON:H+ | 0.196* | 0.377** | 0.586*** | ns | ns |
DOC:Al | 0.715*** | 0.593*** | 0.614*** | 0.382** | |
DON:Al | 0.355* | 0.610*** | ns | 0.324* | |
Al:H+ | 0.478*** | 0.745*** | 0.614*** | 0.424** |
DOC and DON were significantly correlated in throughfall, forest floor leachate and topsoil solution (15 cm depth), but not in the deeper soil layers. In all soil compartments, both DOC and DON concentrations were positively related to BC and Al except for DON in SS layer (40 cm depth).
Lastly, we examined the relationships of monthly concentrations between the environmental matrices (Table
Pearson correlation between monthly concentration of NO3, SO4 and DON in throughfall depositions (THR), forest floor leachate (FF), topsoil (TS = topsoil solution at 15 cm depth), subsoil (SS = subsoil solution at 40 cm depth) and deep soil (DS = deep soil solution at 70 cm depth). Significance: * = p ≤ 0.05; ** = p ≤ 0.01; *** = p ≤ 0.001; ns: not significant.
NO3 | SO4 | DON | |
---|---|---|---|
THR : FF | 0.603*** | 0.577*** | 0.480*** |
THR : TS | 0.710*** | 0.599*** | ns |
THR : SS | 0.404*** | 0.447*** | 0.360** |
THR : DS | 0.387*** | 0.335** | 0.282 |
FF : TS | 0.397*** | 0.249* | ns |
FF : SS | 0.242* | ns | ns |
FF : DS | 0.477*** | 0.380** | ns |
TS : SS | 0.603*** | 0.768*** | ns |
TS : DS | 0.534*** | 0.438*** | ns |
SS : DS | 0.508*** | 0.525*** | ns |
The influence of air temperature (minimum, maximum and mean), the amount of throughfall precipitation and snow (spring and total winter snow) on the concentration of the main chemical species was investigated at interannual scale.
The annual throughfall concentrations of DOC, DON, NO3 were negatively linearly related to the amount of rain (Figure
Relationship between the amount of precipitation (mm yr-1) and the concentrations of NO3, DON and DOC in the throughfall (mg L-1).
Likely, DOC concentration in the forest floor leachates significantly decreased at the increasing of the throughfall precipitation (Suppl. material
The air temperature descriptors had no influence on the chemistry of the investigated environmental compartments.
The monthly volume-weighted average concentrations of both inorganic and organic species in throughfall deposition show their maximum from March to the end of summer and minimum values in autumn and winter (Figure
Box&Wisker showing the monthly variations of the NO3, DON and DOC concentrations in the throughfall deposition.
Despite high variability, a seasonal variation was quite evident for NH4 and NO3 in forest floor leachate with higher concentrations in warmer months (Figure
Box & Wisker showing the monthly variations of NO3 and NH4 concentrations in the forest floor leachates (FF).
Throughfall concentrations of NO3 and SO4 significantly declined during the last two decades (1995–2015) unlike NH4 concentration that remained stable (Table
The annual trends of forest floor and mineral soil layers have been estimated over a period ranged from 9 to 13 years, thus shorter than that of throughfall (Table
Mann – Kendall trends for chemical species concentration analyzed in throughfall deposition (THR), forest floor leachate (FF), topsoil (TS = soil solution at 15 cm depth), subsoil (SS = soil solution at 40 cm depth) and deep soil (DS = soil solution at 70 cm depth). Significance of Sen’s slope: *p ≤ 0.05; **p ≤ 0.01; ***p ≤ 0.001; ns: not significant.
Period | H+ | NH4 | NO3 | SO4 | DOC | DON | |||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Slope | % | Slope | % | Slope | % | Slope | % | Slope | % | Slope | % | ||
THR | 1995–2015 | -0.10*** | -3.19 | ns | -0.51*** | -1.44 | -1.37*** | -5.42 | -0.09* | -1.32 | -0.02*** | -3.28 | |
THR | 2005–2015 | -0.05** | -3.08 | ns | ns | -0.80*** | -4.95 | ns | -0.02** | -5.22 | |||
FF | 2006–2015 | 0.30*** | 13.4 | -2.50*** | -8.53 | -2.03** | -6.86 | -1.94*** | -9.21 | ns | ns | ||
TS 15 cm | 2005–2015 | ns | -0.61 | ns | -0.23** | -4.87 | ns | ns | ns | ||||
SS 40 cm | 2005–2015 | ns | 1.12 | -0.10* | -3.78 | ns | -1.67*** | -6.60 | ns | ns | |||
DS 70 cm | 2006–2015 | ns | -1.92 | ns | -0.04* | -2.20 | -1.64*** | -6.45 | -0.13* | -2.47 | 0.01* | 4.04 |
Unlike throughfall, in litter floor leachate H+ increased while BC declined. Trends of DOC and DON concentration in the mineral soil solution resulted statistically significant in the deep soil layer only, and showed slightly declining and increasing values, respectively.
The obtained results highlighted important modifications of the aqueous solution chemistry along the hydrological pathway through different environmental compartments from atmospheric deposition to the forest deep soil.
Particularly, nitrogen species exhibited the greatest quantitative and qualitative variations. Throughfall deposition and forest floor leachates were characterized by similar and comparatively high concentrations of NO3 and NH4, thus being a crucial source of inorganic N for the forest soil. Next, the passage to mineral layers led, for both NO3 and NH4, to a depletion greater than 90%, already in the topsoil (15 cm depth). The analysis of the relationships between chemical species has provided insights on the origin and fate of chemical compounds in the forest ecosystem. The strong positive correlation between NO3 and SO4 in the throughfall deposition suggests common precursors, i.e. SO2 and NOx emitted from anthropogenic sources derived from fossil fuel use. Furthermore, the linear relationship between NH4 and both SO4 and NO3 could be explained considering the formation of ammonium sulfate and nitrate aerosols by a gas-phase reaction of ammonia with sulfuric and nitric acids in the atmosphere (
Contrarily to the organic layer, the mineral soil represents an effective sink of inorganic N at our site, as expected in an N-limited ecosystem like a temperate forest. The potential sink processes of NO3 include assimilation by plant, fungal and bacterial communities (e.g.
The chemical composition of soil solution was used as an indicator of the effects of atmospheric pollution on forest ecosystem as well as to evaluate the efficacy of the flux deposition abatement policies (
The mixture of plant residues from the surrounding canopy and belowground that constitutes the forest floor is the principal source of organic compounds for the forest soil. The concentrations of DOC and DON in the forest floor leachate were 3.5 and 2 folds those measured in the throughfall, which, however, substantially contributes to the soil enrichment. The mean annual concentration of throughfall DOC in the Val Masino plot (6.4±0.8 mg C L-1) was very close to the values reported for spruce forests in the Italian Alps (
Most of infiltrating DOC and DON from the litter floor were retained in the mineral soil. Specifically, DOC concentration decreased to 39% in the topsoil and 31% in the deep soil, while DON reduced correspondingly to 29% and 15%. It is generally assumed that the principal processes responsible for the removal of carbon from the soil solution are abiotic, like precipitation as organo-metal complexes and/or by adsorption to solid Fe and Al phases (
Among the analyzed climatic parameters, the amount of rainfall seems to exert a primary control on DOC and N compounds in throughfall and forest floor leachates. In throughfall, DOC, DON, NO3 and potassium (K) decreased as the amount of rain increased. This suggests a dilution effect occurring especially for chemical species strictly connected with the canopy, species that are washed off during the precipitation events. The decrease of DOC and DON concentrations in forest floor leachates and to a lesser extent also in the topsoil solution indicates that infiltrating water diluted DOC and DON concentrations. This is consistent with the results of
A seasonal effect was evident for NO3, NH4, DON and DOC in the throughfall and, to a lesser extent, for inorganic nitrogen species in litter floor leachates. These findings, at least partly related to temperature, seem to suggest that biological processes occurring in the canopy and the organic soil layer somewhat controlled the N and C concentrations. In the case of throughfall, seasonal changes in the photochemical activity and in the atmospheric stability are to be taken into consideration, too. In the summer, contaminants reach the Val Masino from far away. On the contrary, in the winter the atmospheric deposition contains mostly ions of local origin (
We could not observe an effect of temperature on concentrations of N and C that could explain the yearly variations in all studied ecosystem compartments. The only exception was the positive relationship that linked NH4 in the forest floor leachates to the annual minimum temperature. A regional scale study revealed that fluxes and concentration of DOC and DON were not connected to temperature changes (Michalzik 2001), whereas
The trends rates observed for NO3 and SO4 concentrations in throughfall deposition (-1.4% yr-1 and - 5.4% yr-1, respectively) are in line with those recorded in European forests within the ICP-Forest network (
Trends of NO3 and SO4 in forest floor leachates and mineral soil solution mirrored declining throughfall depositions. NO3 decreased significantly at all depths (with the exception of 40 cm). Especially in the forest floor and topsoil solution the trend rates were higher than those calculated for throughfall deposition. The NO3 trends in mineral soil solution were characterized by elevated concentrations in 2006 and 2007 followed by a drastic decline in the subsequent years (Figure
Annual NO3 concentrations measured in throughfall and forest floor leachates (a) and in the topsoil solution (TS), subsoil solution (SS) and in deep soil solution (DS) (b) during the study period.
Percentage of individual exceedances of the critical limit (CLimE) per year in the topsoil solution (TS), subsoil solution (SS) and deep soil solution (DS) from 2005 to 2015.
A currently debated topic is the influence of atmospheric N deposition loads on the DON losses in forest ecosystems. Some authors recorded an increase of DON and/or a decreasing DOC/DON ratio in soil solution when N loading rates were relatively elevated (
In recent years, the scientific community has been giving greater attention to the effects of reducing atmospheric loads of SO4 on the increasing DOC concentration in surface waters and soil solution in regions that have previously experienced high loads of sulfate (e.g.
The results of the present study confirm the utility of long-term monitoring of additional ecosystem compartments such as soil solution in providing a deeper knowledge of the fate of N and C in the forest ecosystem. The soil solution is a crucial interface connecting the N atmospheric deposition, the terrestrial processes and the streamwater N export. Particularly, the overland flow originating from the forest floor leachate in Val Masino forest represents an important source of inorganic N, which, in certain hydrological conditions, can directly flow to surface waters by-passing the soil layers where the N retention processes take place. The extremely low NO3 concentrations measured in mineral soil solution indicated that a condition of N-limitation occurred independently from the range of N loadings recorded in the study period. The decreasing trend of NO3 in atmospheric deposition observed at our site is in line with observations carried out in other alpine areas. The added value and the uniqueness of this research mainly lies in the evaluation of the response of an alpine forest ecosystem to the reduction of atmospheric pollution, both in temporal and quantitative terms. Contrary to ion species, DOC and DON concentrations do not seem to have been affected by changes in S and N inputs. More in-depth analysis and, possibly, a longer data series will provide a better identification of the most effective factors controlling the dynamic of DOM during the migration through different environmental compartments in the forest ecosystem.
This work was financially supported by ERSAF (Ente Regionale per i Servizi all’Agricoltura e alle Foreste), the EC within the LIFE+ FUTMON project (LIFE07 ENV/D/00218) and the National Research Council – CNR within the MONFOR project. The authors would like to thank the technical staff of the ERSAF headquarters in Morbegno (SO, Italy) for the sampling activities.
Analytical methods, correlation tables and graphs showing additional results
Data type: statistical data